Methods and apparatus for producing alkyl esters from a reaction mixture containing acidified soap stock, alcohol feedstock, and acid

ABSTRACT

Embodiments herein relate to the production of alkyl esters from acidified soap stock. In an embodiment, a process for producing alkyl esters is provided. The process can include mixing acidified soap stock with an alcohol, water, carbon dioxide, and/or carbon monoxide, to form a reaction mixture, and contacting the reaction mixture with a catalyst under supercritical conditions for the alcohol, the catalyst including a metal oxide. Other embodiments are also included herein.

This application claims the benefit of U.S. Provisional Application No.62/627,518, filed Feb. 7, 2018, the content of which is hereinincorporated by reference in its entirety.

FIELD

Embodiments herein relate to the production of alkyl esters fromacidified soap stock. More specifically, embodiments herein relate tomethods and apparatus for producing alkyl esters from acidified soapstock in a reaction mixture containing an alcohol, carbon dioxide (CO₂),carbon monoxide (CO), and/or one or more acids, and a metal oxidecatalyst.

BACKGROUND

Biodiesel is a processed fuel that can be derived from biologicalsources such as refined plant oils. Biodiesel can be utilized alone ormixed with conventional petroleum-based diesel for use in most standarddiesel engines. Biodiesel can also be utilized as a heating fuel incommercial and domestic boilers.

Biodiesel can be considered an environmentally friendly alternative topetroleum-based fossil fuels. For example, use of biodiesel can resultin an overall reduction in greenhouse gas emissions and can be produceddomestically, resulting in a lower dependence on fossil fuel imports.

Biodiesel can contain one or more long-chain fatty acid alkyl esters,including, but not limited to, fatty acid methyl esters, fatty acidethyl esters, fatty acid propyl esters and fatty acid isopropyl estersformed from a transesterification or esterification reaction. Fatty acidalkyl esters can be created from the transesterification oftriglycerides present in plant oil feedstocks and/or animal fatfeedstocks. Fatty acid alkyl esters can also be created from theesterification of free fatty acids present in acidified soap stocks. Theconversion to fatty acid alkyl esters can be produced by catalyzed oruncatalyzed reactions.

Soap stocks can be obtained as a byproduct of crude vegetable oilrefining performed to remove undesired components from the triglyceridefraction of the oils.

SUMMARY

Embodiments herein relate to the production of alkyl esters fromacidified soap stock. More specifically, embodiments herein relate tomethods and apparatus for producing alkyl esters from acidified soapstock in a reaction mixture containing an alcohol, CO₂, CO, and/or oneor more acids, and a metal oxide catalyst.

In an embodiment, a process for producing alkyl esters is provided. Theprocess can include mixing a soap stock and one or more acids to form anacidified soap stock, and then mixing the acidified soap stock with analcohol and carbon dioxide to form a reaction mixture. The process caninclude the step of contacting the reaction mixture with a catalystunder supercritical conditions for the alcohol, where the catalyst canbe a metal oxide.

In some embodiments, the metal oxide catalyst can be selected from thegroup including alumina, titania, zirconia, and hafnia.

In some embodiments, the metal oxide catalyst can include an unmodifiedmetal oxide including alumina, titania, zirconia, and hafnia.

In some embodiments, the metal oxide catalyst can include titania.

In some embodiments, the carbon dioxide can be present in an amountequal to at least 0.1 wt. percent of the mass of the alcohol added.

In some embodiments, the soap stock can include a byproduct derived fromtall oil, rapeseed oil, soybean oil, canola oil, cottonseed oil, grapeseed oil, mustard seed oil, corn oil, linseed oil, sunflower oil,poppy-seed oil, walnut oil, peanut oil, rice bran oil, camellia oil,castor oil, and olive oil, palm kernel oil, coconut oil, rice oil, algaeoil, seaweed oil, or Chinese Tallow tree oil.

In some embodiments, the acidified soap stock can have an acid number ofgreater than or equal to 3 mg KOH/g oil.

In some embodiments, the process can further include the step ofcontacting the reaction mixture with a catalyst to drive the conversionof the acidified soap stock from an acid number of equal to 3 mg KOH/goil to an acid number of less than or equal to 0.5 mg KOH/g oil.

In some embodiments, the process can further include the addition of anorganic acid, a Bronsted acid, or an inorganic acid to the reactionmixture.

In some embodiments, the process can further include mixing an inorganicbase or and organic base into the reaction mixture.

In some embodiments of the process, the step of contacting the reactionmixture with a catalyst can be performed at a temperature of between 200and 400 degrees Celsius.

In some embodiments of the process, the step of contacting the reactionmixture with a catalyst can be performed at a pressure of between 1000and 5000 psi.

In some embodiments of the process, contacting the reaction mixture witha catalyst can be performed with a residence time of less than 60seconds.

In some embodiments of the process, a catalyst having particles with anaverage particle size of 0.2 microns to 2 millimeters can be used.

In some embodiments of the process, a catalyst having a porosity ofbetween 0.3 and 0.6 can be used.

In some embodiments of the process, a catalyst having a pore volume ofbetween 0 and 0.6 ml/gram can be used.

In some embodiments of the process, a particulate metal oxide having asurface area of between 1 and 200 m²/gram can be used.

In some embodiments of the process, a C1-C6 alcohol, such as methanol orethanol, can be used.

In some embodiments, the process can further include the step ofremoving residual free fatty acids from the reaction mixture.

In some embodiments, the process can further include removing residualfree fatty acids from the reaction mixture by adding dimethyl carbonateto the reaction mixture.

In some embodiments, the process can further include removing residualfree fatty acids from the reaction mixture by adsorbing the free fattyacids to a metal oxide substrate and separating the reaction mixturefrom the metal oxide substrate.

In some embodiments, the process can include the production of an amountof alkyl esters that is at least 10% by weight greater than thatproduced by an otherwise identical reaction mixture lacking the carbondioxide and/or one or more acids under the same reaction conditions andresidence time.

In some embodiments, a process for producing alkyl esters is included.The process can include mixing a soap stock and one or more first acidsto form an acidified soap stock, mixing the acidified soap stock with analcohol and a second acid to form a reaction mixture, the second acidincluding carbonic acid and/or one or more organic acids, and contactingthe reaction mixture with a catalyst under supercritical conditions forthe alcohol, the catalyst including a metal oxide selected from thegroup including alumina, titania, zirconia, and hafnia, wherein themetal oxide has been pretreated with a Bronsted acid or a Bronsted base.

In some embodiments, the process can include the use of a metal oxidethat has been pretreated with a Bronsted acid selected from the groupconsisting of hydrobromic acid, hydrochloric acid, hydroiodic acid,nitric acid, sulfuric acid, perchloric acid, boric acid, chloric acid,phosphoric acid, pyrophosphoric acid, methanethiol, chromic acid,permanganic acid, phytic acid and ethylenediamine tetramethyl phosphonicacid (EDTPA).

In some embodiments, a process for producing alkyl esters viaesterification from an acidified soap stock is provided. The process caninclude mixing a soap stock and one or more first acids to form anacidified soap stock, and mixing the acidified soap stock with analcohol and a second acid form a reaction mixture. In some cases, thesecond acid can include carbon dioxide and/or one or more organic acids.The process can also include pumping the reaction mixture into a housingincluding a porous catalyst such that the reaction mixture comes intocontact with the porous catalyst. The porous catalyst can have anaverage particle size of 0.2 microns to 1 millimeter. The temperatureand pressure within the housing can bet set to supercritical conditionsfor the alcohol. In some embodiments, the porous catalyst can include ametal oxide such as one or more of alumina, titania, zirconia, andhafnia. The process can further include collecting a reaction productfrom the housing, where the reaction product can include esters in anamount at least equal to 80% of the free fatty acid or carboxylic acidin the soap stock on a molar basis.

In an embodiment, a process for producing alkyl esters is provided. Theprocess can include mixing a soap stock and one or more acids to form anacidified soap stock, and mixing the acidified soap stock with analcohol and carbon monoxide to form a reaction mixture. The reactionmixture can be contacted with a catalyst under supercritical conditionsfor the alcohol, where the catalyst can include a metal oxide.

In some embodiments of the process, carbon monoxide can be present in anamount equal to at least 0.1 wt. percent of the mass of the alcoholadded.

This summary is an overview of some of the teachings of the presentapplication and is not intended to be an exclusive or exhaustivetreatment of the present subject matter. Further details are found inthe detailed description and appended claims. Other aspects will beapparent to persons skilled in the art upon reading and understandingthe following detailed description and viewing the drawings that form apart thereof, each of which is not to be taken in a limiting sense. Thescope herein is defined by the appended claims and their legalequivalents.

BRIEF DESCRIPTION OF THE FIGURES

Aspects may be more completely understood in connection with thefollowing drawings, in which:

FIG. 1 is a schematic view of an exemplary process in accordance withthe embodiments herein.

FIG. 2 is a schematic view of an exemplary process in accordance withthe embodiments herein.

FIG. 3 is a schematic diagram of a production apparatus in accordancewith the embodiments herein.

While embodiments are susceptible to various modifications andalternative forms, specifics thereof have been shown by way of exampleand drawings, and will be described in detail. It should be understood,however, that the scope herein is not limited to the particularembodiments described. On the contrary, the intention is to covermodifications, equivalents, and alternatives falling within the spiritand scope herein.

DETAILED DESCRIPTION

As discussed above, biodiesel formed from one or more long-chain fattyacid alkyl esters, can be created by the esterification of acidifiedsoap stock feedstocks. The esterification reactions can be catalyzedunder homogeneous or heterogeneous reaction conditions.

Without wishing to be bound by any particular theory, it is believedthat the addition of carbon dioxide (CO₂) and/or carbon monoxide (CO) tothe reaction mixtures described herein can further catalyze theesterification of free fatty acids found in acidulated soap stocks intobiodiesel fuels. It is also believed that addition of CO₂ and/or CO canfurther drive the esterification reactions to completion. In some cases,the acid number can be less than 0.5 (mg KOH/g oil) and specifically asclose to 0 (mg KOH/g oil) as possible.

Referring now to FIG. 1, a schematic view of an exemplary process 100for producing alkyl esters is shown. The process can begin with mixingtogether an acidified soap stock 102, an alcohol feed stock 104, and atleast one of CO₂ 106, CO 107, and/or one or one or more acids 108 toform a reaction mixture at 110. It will be appreciated that in somecases the process can begin with mixing together an acidified soap stock102, an alcohol feed stock 104, and CO₂ 106. In some embodiments, theprocess can begin with mixing together an acidified soap stock 102, analcohol feed stock 104, and one or more acids 108. In yet otherembodiments, the process can begin with mixing together an acidifiedsoap stock 102, and alcohol feed stock 104, CO₂ 106, and one or moreacids 108. In some embodiments, the process can begin with mixingtogether an acidified soap stock 102, an alcohol feed stock 104, and CO107. In yet other embodiments, the process can begin with mixingtogether an acidified soap stock 102, and alcohol feed stock 104, CO107, and one or more acids 108.

It will be appreciated that in some embodiments the reaction mixture cancontain an amount of water suitable to react with CO₂ gas to formcarbonic acid. Without wishing to be bound by any particular theory, itis believed that CO₂ gas dissolves in water to form carbonic acid(H₂CO₃) as follows:CO₂+H₂O↔H₂CO₃

The amount of water suitable for use herein can include the addition ofgreater than or equal to 0.05% by weight (by wt.) water added to thereaction mixture. In some embodiments, the amount of water added to thereaction mixture can include 0.05% by wt., 0.1% by wt., 0.5% by wt.,1.0% by wt., 1.5% by wt., 2% by wt., 3% by wt., 4% by wt., 5% by wt., or10% by wt. It will be appreciated that amount of water added to thereaction mixture can fall within a range, wherein any of the forgoingweight percentages can serve as the lower or upper bound of the range,provided that the lower bound of the range is a value less than theupper bound of the range. It will be appreciated that in someembodiments, gaseous CO₂ can first be passed through water to formcarbonic acid and then mixed into the reaction mixture. In other cases,the CO₂ can be added to the reaction mixture once it reaches the reactor334, as will be discussed further below in reference to FIG. 3. In someembodiments, the water can be introduced into the reaction mixture as acomponent of the alcohols used herein.

It will be appreciated that in some embodiments the reaction mixture cancontain an amount of water vapor suitable for reaction with CO to formCO₂ at the high temperatures and pressures used in the reactions herein.In some cases, CO can be added directly to the reaction mixture. Inother cases, the CO can be added to the reaction mixture once it reachesthe reactor 334, as will be discussed further below in reference to FIG.3. Without wishing to be bound by any particular theory, it is believedthat CO can react with water vapor at high temperatures to form carbondioxide and hydrogen gases.

The acidified soap stock 102 can be derived from various plant oilsources as described more fully below. The alcohol feed stock 104 caninclude one or more types of alcohol as described more fully below. Theone or more acids 108 can include one or more types of acids asdescribed more fully below. In some embodiments, one or more acidifiedsoap stocks, one or more alcohol feed stocks, and CO₂ and/or CO aremixed together to form a reaction mixture. In other embodiments, one ormore acidified soap stocks, one or more alcohol feed stocks, and one ormore acids are mixed together to form a reaction mixture. In yet otherembodiments, one or more acidified soap stocks, one or more alcohol feedstocks, CO₂, CO, and/or one or more acids are mixed together to form areaction mixture.

Mixing the separate components to form a reaction mixture can be done ina separate mixing vessel relative to the vessel containing the separatecomponents, or it can be done by simply injecting one component at atime into the other components until all components are combined. Insome embodiments, the amount of alcohol supplied can be in a molarexcess to the stoichiometric ratio of the reaction. By way of example,for the esterification of a free fatty acid, the stoichiometric ratio is1 moles of alcohol for every 1 mole of free fatty acid. However, thereaction can be pushed farther towards completion by adding a molarexcess of alcohol. In some embodiments, a molar excess of alcohol canalso be supplied to allow for the transesterification of anytriglycerides, monoglycerides, or diglycerides that may present in theacidified soap stock.

Accordingly, in an embodiment, an amount of alcohol can be added to thereaction mixture that exceeds the ratio of 1 parts alcohol to 1 partfree fatty acid. For example, in some embodiments, the amount of alcoholadded to the reaction mixture can be 2 parts alcohol to 1 part freefatty acid. In some embodiments, the amount of alcohol added to thereaction mixture can be 4 parts alcohol to 1 part free fatty acid. Insome embodiments, the amount of alcohol added to the reaction mixturecan be 6 parts alcohol to 1 part free fatty acid. However, in otherembodiments the alcohol can be added to the reaction mixture in a lessthan or equal to the stoichiometric ratio. For example, in someembodiments, the reaction mixture can have a ratio of 0.5-1 moles ofalcohol to 1 mole of free fatty acid.

Similarly, the reaction can be pushed even farther towards completion byadding CO₂ and/or one or more acids to catalyze the esterification offree fatty acids in the reaction mixture. Without wishing to be bound bytheory, it is believed that the addition of CO₂ to the reaction mixturecan result in the formation of carbonic acid (H₂CO₃) due to the reactionbetween CO₂ and water present in the reaction mixture. Carbonic acidand/or one or more additional acids can catalyze the esterification offree fatty acids or otherwise enhance the conversion of free fatty acidsto esters.

In some embodiments, the process can include mixing CO₂ into thereaction mixture in an amount equal to at least 0.1 weight percent (wt.percent or wt. %) of the mass of the alcohol added. In some embodiments,the process can include adding CO₂ in an amount equal to at least 1.0wt. percent of the mass of the alcohol added. In some embodiments, theprocess can include adding CO₂ in an amount equal to at least 0.1 wt. %,1.0 wt. %, 2 wt. %, 3 wt. %, 4 wt. %, 5 wt. %, 6 wt. %, 7 wt. %, 8 wt.%, 9 wt. %, 10 wt. %, 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %, 40 wt. %,or 50 wt. % of the mass of the alcohol added. In some embodiments, anamount of CO₂ can be added to achieve maximum CO₂ solubility in water atthe temperatures and pressures suitable for use in the reactionsdescribed herein. In some embodiments, the reaction mixture can containcarbonic acid at a concentration of at least 0.05, 0.1, 0.25, 0.5, 0.75,1, 1.5, 2, 3, 4, 5, 7.5, 10, 15 or 20 M, or can have a concentrationfalling within a range between any of the foregoing.

The pH of the reaction mixture can vary. In some embodiments, the pH canbe about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 13.5, or thepH can fall within a range between any of the foregoing. In someembodiments, the pH of the reaction mixture can be acidic. In someembodiments, the pH of the reaction mixture can be less than 7. In someembodiments, the pH of the reaction mixture can be less than 3. In someembodiments, the pH of the reaction mixture can be from about 2 to about4.

In some embodiments, the process can include mixing CO into the reactionmixture in an amount equal to at least 0.1 weight percent (wt. percentor wt. %) of the mass of the alcohol added. In some embodiments, theprocess can include adding CO in an amount equal to at least 1.0 wt.percent of the mass of the alcohol added. In some embodiments, theprocess can include adding CO in an amount equal to at least 0.1 wt. %,0.5 wt. %, 1.0 wt. %, 2 wt. %, 3 wt. %, 4 wt. %, 5 wt. %, 6 wt. %, 7 wt.%, 8 wt. %, 9 wt. %, 10 wt. %, 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %,40 wt. %, or 50 wt. % of the mass of the alcohol added. In someembodiments, an amount of CO can be added to achieve maximum COsolubility in water at the temperatures and pressures suitable for usein the reactions described herein.

In some embodiments, the process can include mixing one or more acidsinto the reaction mixture in an amount equal to at least 0.1 weightpercent (wt. percent or wt. %) of the mass of the alcohol added. In someembodiments, the process can include adding one or more acids present inan amount equal to at least 1.0 wt. percent of the mass of the alcoholadded. In some embodiments, the process can include adding one or moreacids present in an amount equal to at least 0.1 wt. %, 1.0 wt. %, 2 wt.%, 3 wt. %, 4 wt. %, 5 wt. %, 6 wt. %, 7 wt. %, 8 wt. %, 9 wt. %, 10 wt.%, 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %, 40 wt. %, or 50 wt. % of themass of the alcohol added.

In some embodiments, the amount of alkyl esters produced by adding CO₂,CO, or one or more acids can be at least 10% by weight greater than thatproduced by an otherwise identical reaction mixture lacking the CO₂, CO,and one or more acids under the same reaction conditions and residencetime.

In some embodiments, the reaction mixture can include one or moreorganic bases or inorganic bases to further catalyze thetransesterification of triglycerides to completion. In some embodiments,the reaction mixture can include a Lewis base. Some examples forsuitable Lewis bases can include anions formed from the dissociation ofacids such as hydrobromic acid, hydrochloric acid, hydroiodic acid,nitric acid, sulfuric acid, perchloric acid, boric acid, chloric acid,phosphoric acid, pyrophosphoric acid, chromic acid, permanganic acid,phytic acid and ethylenediamine tetramethyl phosphonic acid (EDTPA), andthe like. Other Lewis bases can include, but not be limited hydroxideion as formed from the dissociation of bases such as sodium hydroxide,potassium hydroxide, lithium hydroxide and the like. Suitable inorganicbases can include, but not be limited to lithium hydroxide, sodiumhydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide,and barium hydroxide, and the like.

In some embodiments, the reaction mixture can also include a carriercompound. A carrier compound can serve various purposes includinghelping to reduce the viscosity of the reaction mixture. The carriercompound can be a compound that is non-reactive under the reactionconditions. Examples of carrier compounds can include, but are notlimited to, hexane, saturated cycloalkanes, and fluorinatedhydrocarbons. Carrier compounds can be present in the reaction mixturein an amount from 0.0 wt. % to 99.9 wt. %. Conversely, activecomponents, such as an acidified soap stock and the alcohol feed stockcan be present in the reaction mixture in an amount from 0.1 wt. % to100.0 wt. %.

After mixing all components together to form a reaction mixture, thereaction mixture can be contacted with a catalyst at 112. In someembodiments, the catalyst can be a metal oxide catalyst. Suitable metaloxide catalysts for use herein are described more fully below. In someembodiments, step of contacting the reaction mixture with a metalcatalyst can include contacting the reaction mixture with a catalystunder supercritical conditions for the alcohol. In some embodiments,step of contacting the reaction mixture with a metal catalyst caninclude contacting the reaction mixture with a catalyst undersupercritical conditions for CO₂.

In some embodiments, the metal oxide catalyst can have an acid or baseadsorbed thereto. In some embodiments, the metal oxide can be unmodifiedand does not have an acid or base adsorbed thereto. In some embodiments,the metal oxide catalyst can be disposed within a reactor having ahousing. By way of example, the metal oxide catalyst can be disposedwithin a column. The metal oxide catalyst can be packed within thehousing such that the reaction mixture must pass between particles ofthe metal oxide catalyst as it passes through the housing. The housingcan be constructed to withstand the high pressures and temperaturesassociated with supercritical conditions of water, alcohols, and CO₂,and CO. Supercritical conditions suitable for use herein are discussedfurther below.

After the reaction mixture is passed over the metal oxide catalyst andthe reaction is driven to a desired degree of completion, the reactionproducts in the effluent from the reaction can be separated from oneanother at 114. In some embodiments, the main fraction is an alkyl esterfraction, which can be stored in a storage tank or it can be immediatelyutilized as biodiesel in a diesel engine. Additional byproducts of thereaction can be further separated from the rest of the reactionproducts. By way of example, in some embodiments, the reaction producesglycerol as a byproduct. It will be appreciated that as used herein theterms “glycerol”, “glycerine” and “glycerin” are all equivalent. Theglycerol can be readily separated from the alkyl esters, since glycerolhas a tendency to phase separate from alkyl esters making the separationprocess relatively straightforward. Various types of separation devicescan be used, such as a centrifugal fluid separator or the like.Additional reaction products can include aldehydes and ethers, such asdimethyl ether. The glycerol and other reaction products can be storedand later sold, used as a feed stock for other chemical processes, usedas a feedstuff for animals, or used for human foods after furtherpurification.

In some embodiments, the method may optionally include a step ofremoving free fatty acids from the reaction mixture, if present, at 116.This step of removing free fatty acids can also be referred to as a“polishing” step. This can be performed at various points in theproduction process such as before or after the step of separatingreaction product at 114 and/or before or after passing the reactionmixture over the catalyst at 112.

In some embodiments, removing residual free fatty acids from thereaction mixture can include adding a compound to the reaction mixturethat serves to react with the residual free fatty acids. Such ascompound can be referred to as a residual free fatty acid scavenger orscavenging compound. An exemplary scavenging compound for this purposeis dimethyl carbonate. However, other compounds can also be used as ascavenging compound. In some embodiments, the scavenging compound can beadded to the reaction mixture before contacting the reaction mixturewith the catalyst. In other embodiments, the scavenging compound can beadded after the transesterification reaction has taken place.

In some other embodiments, the residual free fatty acids in the reactionmixture can be removed in other ways. For example, a material can beused to absorb residual free fatty acids compounds. Specifically, metaloxide media containing acid/base surface properties such as Lewis acidsites, Bronsted base sites, and/or Bronsted acid sites can be used toselectively bind, at relatively low temperatures, and remove organicacids from fatty acid alkyl ester reaction products. This can beperformed in various ways. In an embodiment, an appropriate metal oxidemedia can be disposed within the interior volume of a housing. A crudereaction product mixture containing free fatty acids can then be pumpedinto the housing. After contacting the metal oxide media, free fattyacids in the crude reaction product mixture can be bound to the metaloxide media. Next, the purified reaction product mixture can beseparated out, leaving behind the metal oxide media and bound organicacids.

In some embodiments, the reaction can be performed under conditionssufficient to result in the production of aldehydes and/or ethers as adecomposition byproduct of glycerol instead of glycerol itself. In someembodiments, the reaction products include gases, such as dimethylether. While not intending to be bound by theory, the production ofgases as a byproduct can be advantageous because it is believed to beeasier to separate various gases from fatty acid alkyl esters than it isto separate out glycerol from fatty acid alkyl esters.

Depending on the specific metal oxide used to catalyze the reaction offree fatty acids to form alkyl esters, a need may arise to periodicallyreprocess the catalyst. For example, in the context of modified metaloxide catalysts, the catalyst can be periodically retreated with an acid(such as sulfuric acid or phosphoric acid) or a base (such as sodiumhydroxide). In the context of a continuous flow production facility,stopping production to reprocess the catalyst or to replace the catalystmay be costly and inefficient. As such, in some embodiments, at leasttwo different reactors can be included such that feed stock flow can bediverted back and forth between the reactors so that one can be taken“off-line” and recharged without interrupting the production process.After the particular reactor is recharged, such as through treatmentwith an acid or a base, it can be returned to service.

Because the reaction mixture is passed over a metal oxide catalyst at anelevated temperature, there is a need to dissipate heat after thereaction has gone to completion. In an embodiment, heat from theeffluent products is used to heat up the acidified soap stock, alcoholfeed stock, CO₂, CO, and/or acid through a counter-flow heat exchanger.Transferring heat from the effluent flow to the feed stock flow can makethe alkyl ester production process more energy efficient since lessenergy is used to get the reaction mixture up to the desired temperatureand promotes the mixing of the reactants for faster conversion withinthe continuous reactor. In some embodiments the reactor housing can be aceramic that can withstand elevated temperatures and pressures. In someembodiments, the housing reactor housing can be a metal or an alloy ofmetals such as INCONEL.

In some embodiments, the reaction mixture reaches the desired level ofreaction completion after one pass over the metal oxide catalyst bed orpacking. However, in some embodiments, the effluent flow may be reroutedover the same metal oxide catalyst or routed over another metal oxidecatalyst bed or packing so that reaction is pushed farther towardcompletion in measured stages.

In some embodiments two or more reactors having metal oxide catalystbeds disposed therein can be used to convert one or more acidified soapstocks to alkyl esters. For example, in some embodiments, a reactionmixture can be passed through both an acid-modified metal oxide catalystbed and a base-modified metal oxide catalyst bed in succession. Thereaction temperatures within each catalyst bed can be either the same ordifferent. In a particular embodiment, a reaction mixture is firstpassed through an acid-modified metal oxide catalyst bed at a relativelylower temperature and then passed through a base-modified metal oxidecatalyst bed at a relatively higher temperature. The acid-modifiedcatalyst reaction step can serve to reduce the amount of free fattyacids in the reaction mixture before it is passed on to thebase-modified catalyst reaction step.

In some embodiments, an acid-modified metal oxide catalyst (such assulfuric or phosphoric acid modified) and a base-modified metal oxidecatalyst (such as sodium hydroxide modified) can be separately formedbut then disposed together within a housing. In such an approach, thereaction mixture passing through the housing can be simultaneouslyexposed to both the acid and base modified metal oxide catalysts.

In some embodiments, two different metal oxides (such zirconia andtitania) can be separately formed but then disposed together within areactor housing. In such an approach, the reaction mixture passingthrough the housing can be simultaneously exposed to both metal oxidecatalysts.

It will be appreciated that the process 100 shown in FIG. 1 can beconducted in a continuous flow mode. By way of example, the process 100can be carried out such that all of the steps are taking placesimultaneously and the feedstocks, CO₂, CO, and/or one or more acids arecontinuously being resupplied and turned into biodiesel fuel. While notintending to be bound by theory, continuous flow production of biodieselfuel can offer substantial advantages over batch production, includingbeing more economical. However, in another embodiment, the flow may beperiodically stopped to allow for the reaction to proceed to completionand then turned back on to continue the production cycle. This processof stopping and restarting flow can be referred to as a semi-continuousflow mode.

Referring now to FIG. 2, a schematic view is shown of a method 200 ofproducing alkyl esters in accordance with the embodiments herein.Reactant materials (such one or more acidified soap stocks, one or morealcohol feed stocks, CO₂, CO, and/or one or more acids) can be stored intanks before being used at 202. In some embodiments each reactant can bestored in individual tanks. In other embodiments, the reactants can bemixed within the same tank. The tanks can be heated or unheated. Thereactant materials can be pumped at a high pressure at 204. The highpressure can be sufficient to prevent vaporization of the feed stockmaterials and acids at the temperature of the reaction. Next, the feedstock materials and acids can be reacted in order to produce a reactionproduct composition that can include alkyl esters (such as biodieselfuel) and byproducts (including aldehydes, ethers, and glycerol) at 206.After the reaction goes to completion, any volatile materials (such asleft over alcohol or other organic compounds) and byproduct gases (suchas ethers) are removed from the reaction product composition at 208. Anyremaining byproducts (such as glycerol) can be separated from the alkylesters (such as biodiesel fuel) at 210. Finally, end products such asalkyl esters and byproducts such as glycerol can be stored until beingused in other processes or until being shipped away from the productionplant at 212.

Referring now to FIG. 3, a schematic diagram is shown of an alkyl esterproduction apparatus 300 for producing alkyl esters in accordance withthe embodiments herein. An acidified soap stock can be held in acidifiedsoap stock tank 302. In some embodiments, the acidified soap stock tank302 can be heated. In some embodiments, the acidified soap stock tank302 can maintain the acidified soap stock at a temperature high enoughto keep the acidified soap stock in a liquid state prior to forming areaction mixture with other reactants. Upon exit from acidified soapstock tank 302, the acidified soap stock can pass through a soap stockpump 310 before passing through a heat exchanger 318 where it can absorbheat from downstream products.

An alcohol feed stock can be held in an alcohol tank 304. In someembodiments, the alcohol tank 304 can be heated. Upon exit from thealcohol tank 304, the alcohol feed stock can pass through an alcoholpump 312 before passing through a heat exchanger 318 where it can absorbheat from downstream products or from a pre-heater (not shown). The CO₂can be held in a pressurized tank 306 and the CO can be held in apressurized tank 307. The CO₂ can pass through a back pressure regulator314 before passing through a heat exchanger 318 where it can absorb heatfrom downstream products from a pre-heater (not shown). The CO can passthrough a back pressure regulator 315 before passing through a heatexchanger 318 where it can absorb heat from downstream products from apre-heater (not shown).

One or more acids can be held in acid tank 308. In some embodiments, theacid tank 308 can be heated. The acid can pass through an acid pump 316before passing through a heat exchanger 318 where it can absorb heatfrom downstream products from a pre-heater (not shown). In someembodiments, the heat exchanger 318 is a counter-flow heat exchanger.

An exemplary counter-flow heat exchanger is described in U.S. Pat. No.6,666,074, the contents of which are herein incorporated by reference.For example, a pipe or tube containing the effluent flow can be routedpast a pipe or tube holding the feed stock flow or the reaction mixture.In some embodiments, a pipe-in-pipe counter-flow heat exchanger can beused. In some embodiments, a thermally conductive material, such as ametal, connects the effluent flow with the feed stock flow so that heatcan be efficiently transferred from the effluent products to the feedstocks or the reaction mixture.

While FIG. 3 shows CO₂ added as a separate reactant in parallel withother reactant materials, it will be appreciated that CO₂ canalternatively be mixed directly into one or more reaction tanks,including acidified soap stock tank 302, alcohol tank 304, or acid tank308. For example, in some embodiments, the CO₂ can be added directly tothe alcohol tank 304. In other embodiments, the CO₂ can be addeddirectly to a reaction mixture in the reactor 334. Similarly, while FIG.3 shows CO added as a separate reactant in parallel with other reactantmaterials, it will be appreciated that CO can alternatively be mixeddirectly into one or more reaction tanks, including acidified soap stocktank 302, alcohol tank 304, or acid tank 308. For example, in someembodiments, the CO can be added directly to alcohol tank 304. In otherembodiments, the CO can be added directly to a reaction mixture in thereactor 334.

It will be appreciated that the feed stock tanks described herein canoptionally include an agitation mechanism and temperature controlmechanism to keep the components in the tanks thoroughly mixed and at arelatively constant temperature. In some embodiments, one or all of theacidified soap stock, alcohol, or acid feed stock tanks may include agas sparger/bubbler so as to displace dissolved oxygen to avoid anyoxidation reactions that can potentially occur at high temperatures. Insome embodiments, the tank(s) can be continuously sparged with an inertgas, such as nitrogen, to remove dissolved oxygen from the feed stocks.In some embodiments, sparging the tank(s) with nitrogen gas can furtherlimit potential oxidation reactions. Although the acidified soap stock,the alcohol feed stock, the CO₂, and/or the acid feed stock in theembodiment shown in FIG. 3 are in different tanks, it will beappreciated that in some embodiments they can be disposed in the sametank.

In some embodiments the feed stocks, such as the acidified soap stock,can be processed in order to remove particulate matter and other debrisbefore being processed through the reactor 334. By way of example, thefeed stocks can be filtered or distilled. In some embodiments the feedstocks can be processed with a continuous centrifuge that can spin outall particulates and in some cases even water from the acidified soapstock.

After passing through the heat exchanger 318, the acidified soap stockpasses through a shutoff valve 320 and a filter 322 to removeparticulate material of a certain size from the feed stock. Similarly,the alcohol feed stock passes through a shutoff valve 324 and a filter326, and the acid feed stock passes through shutoff valve 328 and filter330. The acidified soap stock, alcohol feed stock, CO₂, and/or acid feedstock then pass through a preheater 332 where they are mixed together toform a reaction mixture. The preheater 332 can elevate the temperatureof the reaction mixture to a desired level. Many different types ofheaters are known in the art and can be used.

It will be appreciated that while acidified soap stock, alcohol feedstock, CO₂, CO, and/or acid feed stock are shown in FIG. 3 as passingthrough separate shutoff valves and filters, they can also mix withinthe heat exchanger 318 and exit such that the reaction mixturecontaining acidified soap stock, alcohol feed stock, and CO₂, CO, and/oracid feed stock can pass through a single shutoff valve and filtersequence (not shown).

In some embodiments, a pre-heating step can be performed to raise thetemperature of the reactants before they enter a reactor housingcontaining the metal oxide catalyst. Preheating of the reactants can beperformed in various ways including using a heating block, a heatingbath, a counter-current heat exchanger, etc. While not intending to bebound by theory, it is believed that pre-heating the reactants canimprove the efficiency of the reaction in part because of the effectpre-heating has on the maintenance of temperatures within the reactorhousing. In some embodiments, the reactants can be preheated to at leastabout 70% of the reaction temperature inside of the reactor housingcontaining the metal oxide catalyst. In some embodiments, the reactantscan be preheated to at least about 80% of the reaction temperatureinside of the reactor housing containing the metal oxide catalyst. Insome embodiments, the reactants can be preheated to at least about 90%of the reaction temperature inside of the reactor housing containing themetal oxide catalyst. In some embodiments, reactants can be preheated toat least about 95% of the reaction temperature inside of the reactorhousing containing the metal oxide catalyst. In some embodiments,reactants can be preheated to substantially the same temperature as thereaction temperature inside of the reactor housing containing the metaloxide catalyst. In some embodiments, reactants can be preheated to atemperature higher than the reaction temperature inside of the reactorhousing containing the metal oxide catalyst. In some cases, thereactants are raised to supercritical conditions for temperature andpressure for the alcohol feed stock before entering the inside of thereactor housing. In some cases, the reactants are raised tosupercritical conditions for temperature and pressure for the CO₂ or oneor more acids before entering the inside of the reactor housing.

After preheating, the reaction mixture can then pass through a reactor334 where the reaction mixture is converted into alkyl esters forming areaction product mixture. The reactor 334 can include a metal oxidecatalyst. For example, the reactor can include an acid (such as sulfuricacid or phosphoric acid) modified or base (such as sodium hydroxide)modified metal oxide catalyst, or an unmodified metal oxide catalyst.The reaction product mixture can pass through a backpressure regulator336 and the heat exchanger 318 before passing on to a distillationapparatus 338. The distillation apparatus 338 can be configured to carryout fractional distillation in order to remove excess alcohol from thereaction product mixture and/or isolate one or more fractions of thebiodiesel fuel that meets ASTM specifications. The distillationapparatus 338 can include any desired number of theoretical plates inorder to recover a desired amount of the excess alcohol and to removeany other byproducts of the reaction. In some embodiments, the recoveredalcohol can be de-watered by using molecular sieves. In someembodiments, the alcohol recovered from distillation can be put backinto the alcohol tank 304 for reuse.

In many embodiments, the reaction mixture is maintained at an elevatedtemperature within the reactor. The reactor can be configured towithstand the temperature and pressure under which the reaction mixtureis kept. In some embodiments, a heating element is in thermalcommunication with the reactor so as to be able to heat the reactionmixture up to the desired temperature. If the temperature of thereaction mixture is not sufficiently high, the reaction may proceed moreslowly than desired. In some embodiments, the temperature of thereaction mixture is maintained at a temperature of between 200° and 400°Celsius. In some embodiments, the temperature of the reaction mixture ismaintained at a temperature of between 100° and 600° Celsius. In someembodiments, the temperature of the reaction mixture is maintained at atemperature of between 350° and 400° Celsius.

In some embodiments, the temperature of the reaction mixture is about50°, 75°, 100°, 125°, 150°, 175°, 200°, 225°, 250°, 275°, 300°, 325°,350°, 375°, 400°, 425°, 450°, 475°, 500°, 525°, 550°, 575°, 600°, 625°,650°, 675° Celsius or hotter. It will be appreciated that temperature ofthe reaction mixture can fall within a range, wherein any of theforgoing temperatures can serve as the lower or upper bound of therange, provided that the lower bound of the range is a value less thanthe upper bound of the range. In some embodiments, the temperature ofthe reaction mixture can be greater than the critical temperature of thealcohol feed stock. In some embodiments, the temperature of the reactionmixture can be greater than the critical temperature of the CO₂ or oneor more acids.

Supercritical conditions for water can include a temperature (T) of≥350° Celsius and pressure (P) of ≥3200 psi. Supercritical conditionsfor the alcohols described herein can include supercritical conditionsfor methanol (T≥240° Celsius and P≥1150 psi) and supercriticalconditions for ethanol (T≥240° Celsius and P≥890 psi). Supercriticalconditions for CO² can include a T≥30° Celsius and P≥105 psi.Supercritical conditions for CO can include a T≥−140° Celsius and P≥507psi.

However, in some embodiments, the temperature of the reaction mixturecan be less than about 500° Celsius. In some embodiments, thetemperature of the reaction mixture can be less than about 400° Celsius.

In some embodiments, the reaction mixture is kept under pressure. Thereactor can be configured to withstand the pressure under which thereaction mixture is kept. A desirable pressure for the reaction mixturecan be estimated with the aid of the Clausius-Clapeyron equation.Specifically, the Clausius-Clapeyron equation can be used to estimatethe vapor pressures of a liquid. The Clausius-Clapeyron equation is asfollows:

${\ln\left( \frac{P_{1}}{P_{2}} \right)} = {\frac{\Delta\; H_{vap}}{R}\left( {\frac{1}{T_{2}} - \frac{1}{T_{1}}} \right)}$

wherein ΔH_(vap)=is the enthalpy of vaporization; P₁ is the vaporpressure of a liquid at temperature T₁; P₂ is the vapor pressure of aliquid at temperature T₂, and R is the ideal gas law constant.

In some embodiments, the pressure inside the reactor can be greater thanthe vapor pressures of any of the components of the reaction mixture. Insome embodiments, the pressure inside the reactor can be greater thanabout 500 psi, 600 psi, 700 psi, 800 psi, 900 psi, 1000 psi, 1250 psi,1500 psi, 1750 psi, 2000 psi, 2250 psi, 2500 psi, 2750 psi, 3000 psi,3250 psi, 3500 psi, 3750 psi, 4000 psi, 4250 psi, 4500 psi, 4750 psi,5000 psi, 5250 psi, 5500 psi, 5750 psi, 6000 psi, 6250 psi, 6500 psi,6750 psi, 7000 psi or higher. In some embodiments, the pressure isbetween about 1000 psi and about 5000 psi. In some embodiments, thepressure is between about 1500 psi and about 3500 psi. In someembodiments, the pressure is between about 500 psi and about 2000 psi.In some embodiments, the pressure inside the reactor is greater than thecritical pressure of the alcohol used in the reaction. In someembodiments, the pressure inside the reactor is greater than thecritical pressure of CO₂ or one or more acids used in the reaction.

The reaction mixture may be passed over the metal oxide catalyst withinthe reactor for a length of time sufficient for the reaction to reach adesired level of completion. This will in turn depend on various factorsincluding the temperature of the reaction, the chemical nature of thecatalyst, the surface area of the catalyst, and the like. The term“residence time” can be used to describe the amount of time in which thereaction product mixture interacts with the catalyst in the reactor.Embodiments herein can include methods and systems wherein the residencetime is relatively small while still achieving high percentages ofconversion. By way of example, in some embodiments the residence time isless than about 60 seconds. In some embodiment, the residence time isless than about 30 seconds. In some embodiment, the residence time isless than about 10 seconds.

The remaining reaction products can then pass on to a stirred tank 340where, in some embodiments, the remaining reaction products are mixedwith a base solution, such as a sodium hydroxide solution, from a basesolution tank 342. The base solution can react with remaining free fattyacids in order to convert them (saponification) into a soap composition.However, it will be appreciated that in other embodiments the residualfree fatty acids are removed using other methods such as those describedwith respect to FIG. 1 above.

The remaining reaction products and the soap composition can then passon to a separation apparatus 344 that is configured to separatebyproducts such as glycerol and the soap composition from the alkylesters (such as biodiesel). The alkyl esters can be passed into an alkylester storage tank 346. The soap composition and the glycerol are can bepassed into a byproduct tank 348.

In some embodiments (not shown), a metal oxide can be used as a scrubberto reduce or eliminate certain components from a reaction mixture orfeed stock. By way of example, in some embodiments, unmodified zirconia,titania, and/or hafnia can be used to remove free fatty acids fromcompositions before or after the reaction that produces fatty acidmethyl esters. As discussed above, it is believed that free fatty acidscan be adsorbed to such metal oxides and therefore removed from thereaction mixture or reaction products.

One advantage of biodiesel fuel is that it can be used to operateexisting diesel engines. The proper performance of diesel enginesdepends on a degree of consistency in the diesel fuel itself. However,various factors can affect the consistency of the fuel made bytransesterification including the specific feed stocks used, theparticular separation steps used, and the type of catalysis used. Forthese reasons, the American Society for Testing and Materials (ASTM) hascreated a standard for biodiesel fuel (ASTM D6751-06a). Embodimentsherein can be used to produce a mixture of alkyl esters that meets thespecifications of ASTM D6751-06a. Specifically, embodiments herein caninclude alkyl ester solutions complying with ASTM D6751-06a.

Embodiments can also include a diesel fuel composition including fattyacid alkyl esters as the reaction product of fatty acids from anacidified soap stock, an alcohol feedstock, CO₂, CO, and/or an acid,wherein at least about 50%, 60%, 70%, 75%, 80%, 85%, 90%, 95%, 97%, 98%,or 99% of the free fatty acids on a molar basis are converted into fattyacid methyl esters.

Soap Stocks

Soap stocks suitable for use as feed stocks herein can be obtained as abyproduct of crude vegetable oil refining performed to remove undesiredcomponents from the triglyceride fraction of the oils. Soap stocks caninclude, but not be limited to water, free fatty acids, sodium orpotassium soaps of fatty acids, phospholipids, waxes, aldehydes,ketones, mono glycerides, diglycerides, and triglycerides and otherfatty compounds. In some embodiments, soap stocks can be rich in freefatty acids and can be a valuable source for biodiesel applications.

Feed stocks suitable for use herein can include soap stock andacidulated soap stock. Acidulation of soap stock to recover the acidoils therein can include adding a strong mineral acid, such as sulfuricacid, to raw a soap stock and allowing the free fatty acids to bereleased into solution. In some embodiments, the acid used foracidulation of one or more soap stocks can include other strong acidssuch as nitric acid, hydrochloric acid, phosphoric acid, perchloricacid, hydrobromic acid, hydroiodic acid, etc. In some embodiments, theacidulation can be performed at a relatively low pH at or near pH 2 topH. In some embodiments, the pH can be close to pH 4.

Soap stocks suitable for use with the embodiments herein can be derivedfrom many different plant sources. In some embodiments, soap stocks caninclude lipids (e.g., fats or oils) produced from processing any type ofland-dwelling or water-dwelling plant. In an embodiment, the soap stocksused can include triglycerides. Many different biological soap stocksderived from plants can be used. By way of example, plant-based soapstocks can include rapeseed oil, soybean oil (including degummed soybeanoil), canola oil, cottonseed oil, grape seed oil, mustard seed oil, cornoil, linseed oil, safflower oil, sunflower oil, poppy-seed oil, pecanoil, walnut oil, oat oil, peanut oil, rice bran oil, camellia oil,castor oil, and olive oil, palm oil, coconut oil, rice oil, algae oil,seaweed oil, Chinese Tallow tree oil. Other plant-based biological soapstocks can be obtained from argan, avocado, babassu palm, balanites,borneo tallow nut, brazil nut, calendula, camelina, caryocar, cashewnut, chinese vegetable tallow, cocoa, coffee, cohune palm, coriander,cucurbitaceae, euphorbia, hemp, illipe, jatropha, jojoba, kenaf, kusum,macadamia nuts, mango seed, noog abyssinia, nutmeg, opium poppy,perilla, pili nut, pumpkin seed, rice bran, sacha inche, seje, sesame,shea nut, teased, allanblackia, almond, chaulmoogra, cuphea, jatropacurgas, karanja seed, neem, papaya, tonka bean, tung, and ucuuba,cajuput, clausena anisata, davana, galbanum natural oleoresin, germanchamomile, hexastylis, high-geraniol monarda, juniapa-hinojo sabalero,lupine, Melissa officinalis, milfoil, ninde, patchouli, tarragon, andwormwood.

Acidified soap stocks (also referred to herein as acidulated soapstocks) suitable for use with embodiments herein can specificallyinclude low value soap stocks. Low value soap stocks, generally have arelatively high concentration of free fatty acids. One method ofassessing the concentration of free fatty acids is to determine the acidnumber (or acid value) of the soap stock. The acid number is the mass ofpotassium hydroxide (KOH) in milligrams that is required to neutralizeone gram of the chemical substance being assessed. The precise acidnumber as measured can vary because of the heterogeneity of the soapstock. However, as an example, a high value feed stock such as virginsoybean oil can have an acid number of about 0.35 whereas a lower valuefeed stock can have an acid number of about 5. Yellow grease, a lowvalue feed stock, can have an acid number of about 15 while acidulatedsoap stock, also a low value feed stock, can have an acid number ofabout 88.

Systems and methods herein can advantageously use low value soap stocksin order to produce biodiesel fuel while achieving high percentconversion rates. In some embodiments, the soap stock used has an acidnumber of about 3 (mg KOH/g oil) or greater. In some embodiments, thesoap stock used has an acid number of about 5 (mg KOH/g oil) or greater.In some embodiments, the soap stock used has an acid number of about 10(mg KOH/g oil) or greater. In some embodiments, the soap stock used hasan acid number of about 50 (mg KOH/g oil) or greater. In someembodiments, the soap stock can be converted from one having an acidnumber of greater than or equal to 3 (mg KOH/g oil) to an acid number ofless than or equal to 0.5 (mg KOH/g oil). In some embodiments, the soapstock can be converted from one having an acid number of greater than orequal to 3 (mg KOH/g oil) to an acid number of essentially 0 (mg KOH/goil).

Alcohols

Alcohols suitable for use with the embodiments herein can include manydifferent types of alcohols. By way of example, the alcohols can includethose having from one to six carbon atoms. For example, in someembodiments, methanol is used. Methanol can be advantageous as theresulting alkyl esters (methyl esters) have a lower viscosity thanhigher alkyl esters. However, in some embodiments ethanol is used.Ethanol has low toxicity and is readily produced from plant matter byfermentation processes. In some embodiments, the alcohols suitable foruse herein are around 95% to 97% pure, with the balance being made up ofwater. Without wishing to be bound by theory, it is believed that addingCO₂ to the alcohol feed stock or to the reaction mixture can result inthe formation of carbonic acid within the water fraction of the alcoholfeedstock or the reaction mixture. It is further believed that havingcarbonic acid and/or one or more acids present in the reaction mixturecan increase the rate of esterification and/or transesterification anddrive the reaction to completion such that the acid number is less than0.5. In some embodiments, the reaction can be driven to completion suchthat the acid number is close to zero.

In some embodiments, the alcohols suitable for use herein can includewater present in an amount equal to at least 0.05 wt. %, 0.1 wt. %, 1.0wt. %, 2 wt. %, 3 wt. %, 4 wt. %, 5 wt. %, 6 wt. %, 7 wt. %, 8 wt. %, 9wt. %, 10 wt. %, 15 wt. %, 20 wt. %, 25 wt. %, 30 wt. %, 40 wt. %, or 50wt. % of the mass of the alcohol added. It will be appreciated thatamount of water present in the alcohols suitable for use herein can bewithin a range, wherein any of the forgoing weight percentages can serveas the lower or upper bound of the range, provided that the lower boundof the range is a value less than the upper bound of the range.

In some embodiments, a single alcohol is used. In other embodiments, amixture of different alcohols is used. By way of example, a mixture ofmethanol and a higher molecular weight alcohol can be used. Such amixture can offer the advantage of being more miscible with theacidified soap stock than methanol alone.

Acids

Acids suitable for use with the embodiments herein can include manydifferent types of acids. Without being bound by theory, it is believedthat addition of acid can further catalyze the esterification of freefatty acids present in feed stocks or those that arise from thelipolysis of triglycerides during processing. By way of example, theacids can include one or more of an organic acid, an inorganic acid, aBronsted acid, or a Lewis acid. Suitable organic acids for use hereincan include, but not be limited to formic, acetic, propionic, butyric,valeric, caproic, oxalic, lactic, malic, citric, benzoic, carbonic,phenol, and uric acids, and the like. Suitable inorganic acids for useherein can include, but not be limited to, hydrochloric, nitric,phosphoric, sulfuric, boric, chloric, hydrofluoric, hydrobromic,perchloric, and hydroiodic acids. It will be appreciated that suitableBronsted acids can include any of the forgoing organic acids orinorganic acids. Additional Bronsted acids can be include pyrophosphoricacid, methanethiol, chromic acid, permanganic acid, phytic acid andethylenediamine tetramethyl phosphonic acid (EDTPA). Suitable Lewisacids can include, but not be limited to trimethylamine, tetrhydrofuran,diethylether, acetonitrile, quinuclidine, pyridine, acetone,ethylacetate, dimethylsulfoxide, dimethylacetamide, tetryhydrothiophene,trimethylphosphine, and the like.

Catalysts

Catalysts herein can include those exhibiting sufficient stability inthe presence of supercritical conditions for the alcohols and acidsdescribed herein. For example, the supercritical conditions for methanolinclude T≥240° Celsius and P≥1150 psi and the supercritical conditionsfor ethanol include T≥240° Celsius and P≥890 psi. In some embodiments,the catalysts herein can include those exhibiting sufficient stabilityin the presence of supercritical temperatures and pressures for water(i.e., T≥350° Celsius and P≥3200 psi).

Catalysts herein can include metals, metal oxides, ceramics, and thelike. Catalysts used with embodiments herein can include metal oxideswith surfaces including Lewis acid sites, Bronsted base sites, andBronsted acid sites. By definition, a Lewis acid is an electron pairacceptor. A Bronsted base is a proton acceptor and a Bronsted acid is aproton donor. In some embodiments, the metal oxide catalyst has beenpretreated with a Bronsted acid or a Bronsted base. In some embodiments,the metal oxide catalyst can be treated with a Bronsted, including butnot limited to, hydrobromic acid, hydrochloric acid, hydroiodic acid,nitric acid, sulfuric acid, perchloric acid, boric acid, chloric acid,phosphoric acid, pyrophosphoric acid, methanethiol, chromic acid,permanganic acid, phytic acid and ethylenediamine tetramethyl phosphonicacid (EDTPA).

Catalysts of embodiments herein can specifically include unmodifiedmetal oxides including zirconia, titania, hafnia, yttria, tungsten (VI)oxide, manganese oxide, nickel oxide, nickel, copper oxide, niobiumoxide, cobalt oxide, carbon, carbon/nickel, carbon/platinum. In someembodiments catalysts can include alumina, iron oxide, metal salts,insoluble metal salts, metal oxides, metal hydroxides, metal alloys,metal complexes, and metal ion complexes. Metals of these can includealkali metals, alkaline earth metals, transition metals and poor metals.In some embodiments, the metal can include one or more of group IA, IIA,IIB, IVB, VB, VIB, VIIB, VIIIB, IB, IIB, IIIA, IVA metals. In someembodiments, the catalyst can include one or more of CuO, KH₂PO₄, Nb₂O₅,Y₂O₃, ZnO, MgCO₃, K₂CO₃, Fe₂O₃, and CoO₂. In some embodiments, thecatalyst can consist essentially of one or more of any of the materialsdescribed herein.

In some embodiments, the catalyst can be, or include, a metal oxide thatis stable at temperatures above 250° Celsius in the presence ofsupercritical alcohol. In some embodiments, the catalyst can be, orinclude, a metal oxide that is stable at temperatures above 350° Celsiusin the presence of supercritical alcohol. In some embodiments, thecatalyst can be, or include, a metal oxide that is stable attemperatures above 400° Celsius in the presence of supercriticalalcohol. In some embodiments, the catalyst can be, or include, a metaloxide that is stable at temperatures above 450° Celsius in the presenceof supercritical alcohol. In some embodiments, the catalyst can be, orinclude, a metal oxide that is stable at temperatures above 500° Celsiusin the presence of supercritical water. In some embodiments, thecatalyst can consist essentially of any of the foregoing.

In some embodiments, the catalyst can be, or include, a metal oxide thatis stable at temperatures above 350° Celsius in the presence ofsupercritical water. In some embodiments, the catalyst can be, orinclude, a metal oxide that is stable at temperatures above 400° Celsiusin the presence of supercritical water. In some embodiments, thecatalyst can be, or include, a metal oxide that is stable attemperatures above 450° Celsius in the presence of supercritical water.In some embodiments, the catalyst can be, or include, a metal oxide thatis stable at temperatures above 500° Celsius in the presence ofsupercritical water. In some embodiments, the catalyst can be, orinclude, a metal oxide that is stable at temperatures above 550° Celsiusin the presence of supercritical water. In some embodiments, thecatalyst can consist essentially of any of the foregoing.

Catalysts of embodiments herein can also include silica clad with any ofthe foregoing catalyst materials, such as a metal oxide selected fromthe group consisting of zirconia, titania, hafnia, yttria, tungsten (VI)oxide, manganese oxide, nickel oxide, nickel, copper oxide, niobiumoxide, cobalt oxide, carbon carbon/nickel, carbon/platinum.

In some embodiments, the catalyst can be of a single metal oxide type.By way of example, in some embodiments, the catalyst is substantiallypure zirconia. By way of example, in some embodiments, the catalyst issubstantially pure titania. By way of example, in some embodiments, thecatalyst is substantially pure hafnia. By way of example, in someembodiments, the catalyst is substantially pure yttria. By way ofexample, in some embodiments, the catalyst is substantially puretungsten (VI) oxide. By way of example, in some embodiments, thecatalyst is substantially pure manganese oxide. By way of example, insome embodiments, the catalyst is substantially pure nickel oxide.

Catalysts of embodiments herein can also include mixtures of materials,such as mixtures of materials including zirconia, titania, hafnia,yttria, tungsten (VI) oxide, manganese oxide, nickel oxide, nickel,carbon, carbon/nickel, and carbon/platinum.

In some embodiments, the catalyst can consist essentially of zirconia.Zirconia catalyst particles for use herein can be thermally andchemically stable under supercritical alcohol conditions (e.g., T≥240°Celsius and P≥850 psi). Zirconia catalyst particles for use herein canalso be thermally and chemically stable under supercritical waterconditions (i.e., T≥350° Celsius and P≥3,200 psi). Exemplary zirconiacatalysts are commercially available from ZirChrom Separations of Anoka,Minn. Suitable zirconia catalyst particles for use herein can maintain awell-defined pore structure and are stable under both high pressure(6,000 psi) and high temperature (600° Celsius) conditions. In someembodiments, the zirconia catalyst can be porous and spherical, with anaverage diameter of 25 microns. Zirconia is also well-suited for theembodiments herein due to its high chemical stability over the entire pHrange, from pH of 1 to a pH of 14.

Metal oxide catalysts of embodiments herein can include metal oxideparticles clad with carbon. Carbon clad metal oxide particles can bemade using various techniques such as the procedures described in U.S.Pat. Nos. 5,108,597; 5,254,262; 5,346,619; 5,271,833; and 5,182,016, thecontents of which are herein incorporated by reference. Carbon claddingon metal oxide particles can render the surface of the particles morehydrophobic.

Metal oxide catalysts suitable for use herein can also include polymercoated metal oxides. By way of example, metal oxides herein can includea metal oxide coated with polybutadiene (PBD). Polymer coated metaloxide particles can be made using various techniques such as theprocedure described in Example 1 of U.S. Pub. No. 2005/0118409, thecontent of which is herein incorporated by reference. Polymer coatingson metal oxide particles can render the surface of the particles morehydrophobic.

Metal oxide catalysts of embodiments herein can be made in various ways.As one example, a colloidal dispersion of zirconium dioxide can be spraydried to produce aggregated zirconium dioxide particles. Colloidaldispersions of zirconium dioxide are commercially available from NyacolNano Technologies, Inc., Ashland, Mass. The average diameter ofparticles produced using a spray drying technique can be varied bychanging the spray drying conditions. Examples of spray dryingtechniques are described in U.S. Pat. Nos. 4,138,336 and 5,108,597, thecontents of both of which are herein incorporated by reference. It willbe appreciated that other methods can also be used to create metal oxideparticles. One example is an oil emulsion technique as described inRobichaud et al., Technical Note, “An Improved Oil Emulsion SynthesisMethod for Large, Porous Zirconia Particles for Packed- or Fluidized-BedProtein Chromatography,” Sep. Sci. Technol. 32, 2547-59 (1997). A secondexample is the formation of metal oxide particles by polymer inducedcolloidal aggregation as described in M. J. Annen, R. Kizhappali, P. W.Carr, and A. McCormick, “Development of Porous Zirconia Spheres byPolymerization-Induced Colloid Aggregation-Effect of PolymerizationRate,” J. Mater. Sci. 29, 6123-30 (1994). A polymer induced colloidalaggregation technique is also described in U.S. Pat. No. 5,540,834, thecontents of which are herein incorporated by reference.

Metal oxide catalysts suitable for use with the embodiments herein canbe sintered by heating them in a furnace or other heating device at arelatively high temperature. In some embodiments, the metal oxide issintered at a temperature of about 160° C. or greater. In someembodiments, the metal oxide is sintered at a temperature of about 400°C. or greater. In some embodiments, the metal oxide is sintered at atemperature of about 600° C. or greater. Sintering can be done forvarious amounts of time depending on the desired effect. Sintering canmake metal oxide catalysts more durable. In some embodiments, the metaloxide is sintered for more than about 30 minutes. In some embodiments,the metal oxide is sintered for more than about 3 hours. However,sintering also reduces the surface area. In some embodiments, the metaloxide is sintered for less than about 1 week.

In some embodiments, the catalyst is in the form of particles. Particleswithin a desired size range can be specifically selected for use as acatalyst. For example, particles can be sorted by size using techniquessuch as air classification, elutriation, settling fractionation, ormechanical screening. In some embodiments, the size of the particles isgreater than about 0.2 μm. In some embodiments, the size range selectedis from about 50 nm to about 50 mm. In some embodiments, the size rangeselected is from about 0.2 μm to about 10 mm. In some embodiments, thesize range selected is from about 0.2 μm to about 5 mm. In someembodiments, the size range selected is from about 0.2 μm to about 2 mm.In some embodiments, the size range selected is from about 0.2 μm toabout 1 mm. In some embodiments, the size range selected is from about 1μm to about 100 μm. In some embodiments, the size range selected is fromabout 5 μm to about 15 μm. In some embodiments, the average sizeselected is about 10 μm. In some embodiments the size of the particlesis about 80 μm. In some embodiments the size of the particles is about25-35 μm. In some embodiments, the average size selected is about 5 μm.

In some embodiments, the catalyst can be a particulate in the nanometersize range. In some embodiments, the catalyst can be from about 0.1 nmto about 500 nm. In some embodiments, the catalyst can be from about 1.0nm to about 300 nm. In some embodiments, the catalyst can be from about5.0 nm to about 200 nm. In some embodiments, the catalyst can be used inthe form of a colloid.

In some embodiments, catalyst particles used with embodiments herein canbe porous. By way of example, in some embodiments the particles can havean average pore size of about 30 angstroms to about 2000 angstroms.However, in other embodiments, catalyst particles used are non-porous.

The physical properties of a porous catalyst can be quantitativelydescribed in various ways such as by surface area, pore volume,porosity, and pore diameter. In some embodiments, catalysts ofembodiments herein can have a surface area of between about 1 and about1000 m²/gram. In some embodiments, catalysts of embodiments herein canhave a surface area of between about 1 and about 400 m²/gram. In someembodiments, the catalyst of embodiments herein can have a surface areamuch higher than 400 m²/gram.

In some embodiments, catalysts of embodiments herein can have a surfacearea of between about 1 and about 200 m²/gram. Pore volume refers to theproportion of the total volume taken up by pores in a material perweight amount of the material. In some embodiments, catalysts ofembodiments herein can have a pore volume of between about 0.01 ml/g andabout 2 ml/g. In some embodiments, catalysts of embodiments herein canhave a pore volume of between about 0 ml/gram and 0.6 ml/gram. Porosityrefers to the proportion within a total volume that is taken up bypores. As such, if the total volume of a particle is 1 cm³ and it has aporosity of 0.5, then the volume taken up by pores within the totalvolume is 0.5 cm³. In some embodiments, catalysts of embodiments hereincan have a porosity of between about 0 and about 0.8. In someembodiments, catalysts of embodiments herein can have a porosity ofbetween about 0.3 and 0.6.

Catalyst particles suitable for use with the embodiments herein can havevarious shapes. By way of example, in some embodiments the particle canbe in the form of spherules. In other embodiments, the particle can be amonolith. In some embodiments, the particle can have an irregular shape.

Metal oxides suitable for use with the embodiments herein can includemetal oxides whose surfaces are dominated by Lewis acid-base chemistry.A Lewis acid is an electron pair acceptor. Metal oxides herein can haveLewis acid sites on their surface and can specifically include alumina,zirconia, titania and hafnia. Metal oxides herein can also includesilica clad with a metal oxide selected from the group consisting ofzirconia, alumina, titania, hafnia, zinc oxide, copper oxide, magnesiumoxide and iron oxide. In some embodiments, metal oxides can includeyttria (yttrium oxide), such as ytrria stabilized zirconia. In someembodiments, metal oxides can include magnesium oxide and/or ceriumdioxide. Metal oxides herein can also include mixtures of metal oxides.Specifically metal oxides herein can include mixtures including one ormore of zirconia, alumina, titania and hafnia.

One issue associated with many previous methods for producing biodieselis that the catalysts used are subject to poisoning over time.Specifically, many existing catalysts are affected by the reactionconditions (e.g., pH, temperature, pressure) in a manner so as to reducereaction yield over time. However, some embodiments of metal oxidecatalysts as described herein are advantageous because they are highlyresistant to poisoning over time. This is particularly significant inthe context of supercritical reaction conditions, which may otherwisetend to promote catalyst poisoning. Of the various metal oxides that canbe used with embodiments herein, zirconia, titania and hafnia offerparticular advantages because they are very chemically and thermallystable and can withstand very high temperatures and pressures (such assupercritical conditions for various alcohols) as well as extremes inpH. Such catalysts can exhibit a resistance to poisoning over time. Insome embodiments, the metal oxide catalyst can include zirconia,titania, and/or hafnia. Zirconia and hafnia are even more thermallystable than titania. In some embodiments, the metal oxide catalyst caninclude zirconia and/or hafnia.

Some feed stocks may include components, such as lecithin, that can leadto the deposit of residues resulting in clogging and/or obstruction of atransesterification reactor. The significant thermal stability of metaloxides suitable for use with the embodiments herein can be advantageousin this context because the reactor can be cleaned out through the useof an oxygen containing gas or liquid at extremely high temperatures tocombust any residue that has been deposited on the metal oxide catalyst,thereby cleaning the reactor and returning it to its original state.Other types of catalysts may not have sufficient thermal stability toperform such a cleaning/regeneration process.

In some embodiments, the metal oxides used suitable for use with theembodiments herein can be bare or unmodified. As used herein, the term“unmodified metal oxide” shall refer to a metal oxide that includessubstantially only the metal oxide at its surface, and thus does notinclude significant concentrations of chemical groups such as phosphatesor sulfates on its surface. Many conventional catalyst materials includevarious modifying groups to enhance catalysis. However, as shown in theexamples herein, unmodified metal oxides can surprisingly be used toachieve high conversion percentages and relatively small residencetimes.

However, in other embodiments, metal oxides suitable for use with theembodiments herein can be modified with another compound. For example,the Lewis acid sites on metal oxides herein can interact with Lewisbasic compounds. Thus, metal oxides herein can be modified by adsorbingLewis basic compounds to the surface of metal oxides ntion. A Lewis baseis an electron pair donor. Lewis basic compounds herein can includeanions formed from the dissociation of acids such as hydrobromic acid,hydrochloric acid, hydroiodic acid, nitric acid, sulfuric acid,perchloric acid, boric acid, chloric acid, phosphoric acid,pyrophosphoric acid, methanethiol, chromic acid, permanganic acid,phytic acid and ethylenediamine tetramethyl phosphonic acid (EDTPA).

While not intending to be bound by theory, the use of strong acids as amodifying agent for the metal oxide catalysts herein can be advantageousbecause they absorb more strongly to the Lewis acid sites on the metaloxide and thus be less likely to leach off into the reaction mixture.Exemplary acids include phosphoric acid.

Lewis basic compounds to be used as a modifying agent for the metaloxide catalysts herein can include hydroxide ion as formed from thedissociation of bases such as sodium hydroxide, potassium hydroxide,lithium hydroxide and the like.

The Lewis acid sites on catalysts of embodiments herein can interactwith Lewis basic compounds. Thus, in some embodiments, Lewis basiccompounds can be bonded to the surface of catalysts. However, in otherembodiments, the catalysts used with embodiments herein are unmodifiedand have no Lewis basic compounds bonded thereto. A Lewis base is anelectron pair donor. Lewis basic compounds of embodiments herein caninclude anions formed from the dissociation of acids such as hydrobromicacid, hydrochloric acid, hydroiodic acid, nitric acid, sulfuric acid,perchloric acid, boric acid, chloric acid, phosphoric acid,pyrophosphoric acid, chromic acid, permanganic acid, phytic acid andethylenediamine tetramethyl phosphonic acid (EDTPA), and the like. Lewisbasic compounds of embodiments herein can also include hydroxide ion asformed from the dissociation of bases such as sodium hydroxide,potassium hydroxide, lithium hydroxide and the like.

The anion of an acid can be bonded to a metal oxide of embodimentsherein by refluxing the metal oxide in an acid solution. By way ofexample, metal oxide particles can be refluxed in a solution of sulfuricacid. Alternatively, the anion formed from dissociation of a base, suchas the hydroxide ion formed from dissociation of sodium hydroxide, canbe bonded to a metal oxide by refluxing in a base solution. By way ofexample, metal oxide particles can be refluxed in a solution of sodiumhydroxide. The base or acid modification can be achieved under exposureto the acid or base in either batch or continuous flow conditions whendisposed in a reactor housing at elevated temperature and pressure tospeed up the adsorption/modification process. In some embodiments,fluoride ion, such as formed by the dissociation of sodium fluoride, canbe bonded to the particles.

In some embodiments, catalyst particles can be packed into a housing,such as a column. In some embodiments, the column is a reactor. Themetal oxide particles disposed in a housing can form a fixed-bedreactor. Disposing catalyst particles in a housing is one approach tofacilitating continuous flow processes. Many different techniques can beused for packing the catalyst particles into a housing. The specifictechnique used may depend on factors such as the average particle size,the type of housing used, etc. Generally speaking, particles with anaverage size of about 1-20 microns can be packed under pressure andparticles with an average size larger than 20 microns can be packed bydry-packing/tapping methods or by low pressure slurry packing. In someembodiments, the catalyst particles of embodiments herein can beimpregnated into a membrane, such as a PTFE membrane.

However, in some embodiments, catalysts suitable for use with theembodiments herein are not in particulate form. For example, a layer ofa metal oxide can be disposed on a substrate in order to form acatalyst. The substrate can be a surface that is configured to contactthe feedstocks during processing. In one approach, a catalyst can bedisposed as a layer over a surface of a reactor that contacts thefeedstocks. Alternatively, the catalyst can be embedded as a particulatein the surface of an element that is configured to contact thefeedstocks during processing.

Example 1: Formation of Alkyl Esters

A fixed-bed reactor reaction vessel is packed with a particulate titaniacatalyst. An acidified soap stock is mixed with methanol. Carbon dioxideis added to the mixture. The mixture is pumped under pressure into thefixed-bed reactor reaction vessel. The pressure and temperature in thereaction vessel are supercritical for methanol. The pressure in thereaction vessel is greater than 1154 PSI and the temperature is greaterthan 240 degrees Celsius. A reaction product mixture is obtained. Thereaction product mixture includes alkyl esters.

Example 2: Formation of Alkyl Esters

A fixed-bed reactor reaction vessel is packed with a particulatezirconia catalyst. An acidified soap stock is mixed with ethanol. Carbondioxide is added to the mixture. The mixture is pumped under pressureinto a fixed-bed reactor reaction vessel. The pressure and temperaturein the reaction vessel are supercritical for ethanol. The pressure inthe reaction vessel is greater than 915 PSI and the temperature isgreater than 240.9 degrees Celsius. A reaction product mixture isobtained. The reaction product mixture includes alkyl esters.

It should be noted that, as used in this specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referentsunless the content clearly dictates otherwise. Thus, for example,reference to a composition containing “a compound” includes a mixture oftwo or more compounds. It should also be noted that the term “or” isgenerally employed in its sense including “and/or” unless the contentclearly dictates otherwise.

It should also be noted that, as used in this specification and theappended claims, the phrase “configured” describes a system, apparatus,or other structure that is constructed or configured to perform aparticular task or adopt a particular configuration to. The phrase“configured” can be used interchangeably with other similar phrases suchas arranged and configured, constructed and arranged, constructed,manufactured and arranged, and the like.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated by reference.

The embodiments described herein are not intended to be exhaustive or tolimit the invention to the precise forms disclosed in the followingdetailed description. Rather, the embodiments are chosen and describedso that others skilled in the art can appreciate and understand theprinciples and practices. As such, aspects have been described withreference to various specific and preferred embodiments and techniques.However, it should be understood that many variations and modificationsmay be made while remaining within the spirit and scope herein.

The invention claimed is:
 1. A process for producing alkyl esters comprising: mixing an acidified soap stock with an alcohol, water, carbon dioxide and/or one or more acids to form a reaction mixture; and contacting the reaction mixture with a catalyst under supercritical conditions for the alcohol, the catalyst comprising a metal oxide.
 2. The process of claim 1, the metal oxide selected from the group consisting of alumina, titania, zirconia, and hafnia.
 3. The process of claim 1, the soap stock comprising a byproduct derived from tall oil, rapeseed oil, soybean oil, canola oil, cottonseed oil, grape seed oil, mustard seed oil, corn oil, linseed oil, sunflower oil, poppy-seed oil, walnut oil, peanut oil, rice bran oil, camellia oil, castor oil, and olive oil, palm kernel oil, coconut oil, rice oil, algae oil, seaweed oil, or Chinese Tallow tree oil.
 4. The process of claim 1, the soap stock having an acid number of greater than or equal to 3 mg KOH/g oil.
 5. The process of claim 4, wherein the step of contacting the reaction mixture with a catalyst comprises conversion of the soap stock from an acid number of equal to 3 mg KOH/g oil to an acid number of less than or equal to 0.5 mg KOH/g oil.
 6. The process of claim 1, the acid comprising an organic acid.
 7. The process of claim 1, the acid comprising a Bronsted acid.
 8. The process of claim 1, the acid comprising an inorganic acid.
 9. The process of claim 1, further including mixing an inorganic base or an organic base into the reaction mixture.
 10. The process of claim 1, wherein the step of contacting the reaction mixture with a catalyst is performed at a temperature of between 200 and 400 degrees Celsius.
 11. The process of claim 1, wherein the step of contacting the reaction mixture with a catalyst is performed at a pressure of between 1000 and 5000 psi.
 12. The process of claim 1, the alcohol comprising a C1-C6 alcohol.
 13. The process of claim 1, the alcohol comprising an alcohol selected from the group consisting of methanol and ethanol.
 14. The process of claim 1, wherein carbon dioxide is present in an amount equal to at least 0.1 wt. percent of the mass of the alcohol added.
 15. The process of claim 1, wherein carbon dioxide is present in an amount equal to at least 0.5 wt. percent of the mass of the alcohol added.
 16. The process of claim 1, the reaction mixture comprising carbonic acid.
 17. The process of claim 1, the reaction mixture comprising carbonic acid at concentration of at least 0.05 M.
 18. The process of claim 1, the reaction mixture comprising carbonic acid at concentration of at least 1 M.
 19. The process of claim 1, wherein the pH of the reaction mixture is less than
 7. 20. The process of claim 1, wherein the pH of the reaction mixture is less than
 3. 